Textile decorating composition containing aldehyde-amine resin and zinc silicofluoride cure accelerator



Patented Sept. 14, 1954 TEXTILE DECORATING COMPOSITION CON- TAININGALDEHYDE-AMINE RESIN AND ZINC SILICOFLUORIDE CURE ACCELER- ATOR SamuelLee and Alfred HQSiepert, Fair Lawn, N. J., assignors to InterchemicalCorporation, New York, N. Y., a corporation of Ohio No Drawing.Application May 26, 1950, Serial No. 164,609

2 Claims.

This invention relates to the printing of textile fabrics, and hasparticular reference to a method for simultaneously printing anddischarging previously dyed fabrics by the use of pigmentedwater-in-lacquer emulsions having an inner phase comprising an aqueoussolution of dye discharge agent, the external phases of which comprisewater-immiscible liquids of the filmforming type.

It is known that textile fabrics can be printed by applying water pastesof dyestuffs with watersoluble thickeners to render the compositionsprintable in consistency. The dyes are applied in solution in water andfixed on the fabric in a variety of ways, following which the fabric iswashed to remove thickener, stretched and dried.

When printing on previously dyed cloth it is conventional practice toremove the color from areas to be printed with a decolorizing agent,commonly known as a discharge agent. Since discharge agents, likeprinting pastes, were applied in water solution, the discharging of thecolor did not complicate the printing operation.

In U. S. Patent 2,262,283, issued May 28, 1940, there is disclosed amethod of printingtextile fabrics in which a solution of a dyestuff inwater, generally in the undeveloped state, is emulsified as the innerphase of an emulsion in which the continuous phase is a liquid which isfilm-forming so as to produce an emulsion, and preferably comprising alacquer, i. e., a solution of a filmforming solute in a volatile organicsolvent-to give a paste of printing consistency, and the resulting pasteis then printed onto the fabric. The enveloping of the dyestuii' by thelacquer results in a control of deposition of the color, not previouslyattainable with conventional dye ,pastes. Similarly, U. S. Patents2,222,581-2 disclose a method of printing textiles with pigmentedwater-in-lacquer emulsion.

In U. S. Patent 2,267,620, issued December 23, 1941, there is disclosedthe simultaneous printing and discharging of previously colored textileswith printing pastes obtained by emulsifying a discharge agent into theinterior phase of an emulsion in which the external film-forming lacquerphase is resistant to the action of the discharge agent. Such emulsionsmay be pigmented or they may contain a dyestuif or dyestufi component inthe aqueous phase. Discharge printing with pigmented emulsions of thistype ofiers several advantages over the use of conventional dyestuffs;shades of color not otherwise obtainable can be produced by using thepigmented emulsions, and brighter colors, sharper prints,

and, in many instances, improved permanence, result from dischargeprinting with pigmented emulsions.

Notwithstanding the many advantages to be derived from printing withpigmented or colored emulsions containing a discharge agent, there areseveral disadvantages which have prevented the widespread use of suchemulsions for this type of printing. Some of these difficulties include:low color value of the print due to failure of the resin to adhere tothe fibers of the cloth, breaking of color cuts, gelation of color cuts,and loss of discharge power of cuts on aging.

The present invention is based on the discovery that most of the abovediiiiculties can be substantially completely eliminated by adding awater-soluble metal silicofluoride salt to pigmented emulsionscontaining discharge agents and thermosetting resin to bind the pigmentto the fibers of the cloth. Accordingly, the novel compositions of thepresent invention comprise a pigmented water-in-lacquer emulsioncontaining a water-soluble metal silicofluoride salt and a dischargeagent, preferably a reducing agent, dissolved in the aqueous phase and athermosetting resin dissolved in the lacquer phase. The invention alsocomprehends the novel method of discharge printing using the emulsionsof the present invention.

Typical of the water-soluble metal silicofiuorides which are operable inthe present invention are the zinc, cadmium, mercury, and magnesiumsalts. Ammonium silicofluoride, al-

. though soluble to some extent in watera'nd in many of its reactionsbehaves as a metal salt, technically is not a true metal salt, and isnot operable in the present invention, and hence is not included withinthe scope of the invention. Of the water-soluble metal silicofiuorides,the zinc silicoiiuoride is especially preferred because, among otherreasons, it is readily available at moderate costs, readily soluble inwater to give concentrated solutions (as high as 30% solution at roomtemperature) and exerts a stabilizing influence on the discharge agent.

The water-soluble metal silicofluorides, when used in pigmented printingemulsion containing a thermosetting resin to bind the pigment to thefibers of a cloth and a discharge agent, appear to accelerate the curingor setting of the resin at temperatures conventionally used in the artfor processing textile cloth that has been printed with the emulsion.The silicofluoride accelerator is preferably used in concentration of0.25 to 5.0% by weight of the total emulsion weight.

In preparing a printing paste in accordance with the invention, anaqueous solution of a discharge agent such as sodium hydrosulfite, zinchydrosulfite, sodium sulfoxylate, zinc sulfoxylate, or basic zincsulfoxylate, and a water-soluble metal silicofluoride is emulsified intoa waterimmiscible phase comprising pigment dispersed in a volatile,water-immiscible organic solvent solution of binder resin, including athermosetting resin. If concentrated solutions are used, the emulsionconcentrate which results can be diluted with additional amounts ofvolatile water-immiscible solvent and additional amounts of wateremulsified therein to give an emulsion paste of the desiredconcentration and printing consistency. After cutting with solvent andwater the printing paste should preferably contain from 0.5 to 10% ofbinder resin (up to 5% of which may be thermosetting resin), 5 to 30% ofdischarge agent, 0.25 to 5.0% of water-soluble metal silicofiuoride, andas a practical matter will contain at least about 40% and not more thanabout 80% of aqueous phase.

Printing pastes having this composition can be arrived at by methodsconventional to the art. For instance, the textile printer may besupplied with a concentrated color dispersion consisting of pigmentdispersed in a concentrated lacquer, i. e. a concentrated solution of abinder resin dissolved in a volatile water-insoluble organic solvent.After dilution to the desired concentration, an aqueous solution of adischarge agent may be emulsified into the pigment lacquer and, finally,an aqueous solution of the water-soluble metal silicofluoride isemulsified into the lacquer.

The following examples in which the parts are by weight are given tofurther illustrate the invention.

Example 1 Parts Titanium dioxide 15.0 70% oil modified glycerylphthalate (e. g.

BeckasolP 296) 7.5 Urea -formaldehyde resin (e. g. Beetle in Xylol 33.5Butanol 1.5 20% aqueous solution of basic zinc sulfoxylate 35.0

and 30% aqueous solution of zinc silicofiuoride 5.0

A printing emulsion is prepared from the above ingredients by dispersingthe titanium dioxide pigment in a solution of the glyceryl phthalate andurea-formaldehyde resins in a mixture of the xylol and butanol and thenemulsifying the aqueous solution of basic zinc sulfoxylate and zincsilicofiuorides therein to obtain a water-in-lacquer emulsion. Theresulting emulsion printing paste simultaneously prints white anddischarges colored fabrics dyed with a direct dye, such as an azo dye.

Example 2 Parts Ethyl cellulose lacquer (10% solution of standard ethoxytype, 50100 cp. ethyl cellulose in a solvent consisting of 80 partsXylol and 20 parts pine oil) 12. Mineral spirits 20. 30% aqueoussolution of sodium sulfoxylate 63. 30% aqueous solution of zincsilicofiuoride 5.

A clear emulsion was prepared by diluting the ethyl cellulose lacquerwith the mineral spirits Example 3 Parts 70% drying oil modifiedglycerol phthalate resin, 50% solution in xylol (e. g. Beckasol P 27 5.15% solution of natural rubber, smoked sheet,

in xylol 20. Pine oil 5. Mineral spirits u 15.

30% aqueous solution of sodium hydrosulfate 50. 15% aqueous solution ofmagnesium silicofiuoride 5. Phthalocyanine green dispersion, consistingof 15 parts phthalocyanine green dispersed in 30 parts of Melmac 245-8(50% solution of melamine-formaldehyde resin in equal parts xylol andbutanol) and 55 parts of turpentine 5.

The clear water-in-oil emulsion was prepared by emulsifying the aqueoussolutions of sodium hydrosulfite and magnesium silicofiuoride into themixed solutions of glyceryl phthalate resin and rubber, diluted with thepine oil and mineral spirits. The color dispersion was then added togive a Water-in-oil discharge printing paste that prints a light greenon a dischargeable dark background, such as navy blue.

We claim:

1. A discharge printing paste for textiles comprising a pigmentedwater-in-lacquer emulsion, the outer phase of which comprises apigmented water-immiscible solution of a thermosetting resin of thegroup consisting of urea-formaldehyde resin and melamine-formaldehyderesin in a volatile organic solvent, and the inner phase of which is anaqueous solution of a textile dye discharge agent of the groupconsisting of watersoluble metal hydrosulfites and sulfoxylates and 0.25to 5% of zinc silicofiuoride.

2. A discharge printing paste for textiles comprising a pigmentedwater-in-lacquer emulsion, the outer phase of which comprises awater-immiscible solution of a thermosetting resin of the groupconsisting of urea-formaldehyde resin and melamine-formaldehyde resin ina volatile organic solvent, and the inner phase of which is an aqueoussolution of a textile dye discharge agent of the group consisting ofwater-soluble metal hydrosulfites and sulfoxylates and 0.25 to 5% ofzinc silicofiuoride, wherein the aqueous phase constitutes at least 40%of the emulsion.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,267,620 Cassel Dec. 23, 1941 2,361,277 Enderlin et al. Oct.24, 1944 2,413,624 Harris Dec. 31, 1946 2,555,277 Boyer May 29, 1951

1. A DISCHARGE PRINTING PASTE FOR TEXTILES COMPRISING A PIGMENTEDWATER-IN-LACQUER EMULSION, THE OUTER PHASE OF WHICH COMPRISES APIGMENTED WATER-IMMISCIBLE SOLUTION OF A THERMOSETTING RESIN OF THEGROUP CONSISTING OF UREA-FORMALDEHYDE RESIN AND MELAMINE-FORMALDEHYDERESIN IN A VOLATILE ORGANIC SOLVENT, AND THE INNER PHASE OF WHICH IS ANAQUEOUS SOLUTION OF A TEXTILE DYE DISCHARGE AGENT OF THE GROUPCONSISTING OF WATERSOLUBLE METAL HYDROSULFITES AND SULFOXYLATES AND 0.25TO 5% OF ZINC SILICOFLUORIDE.